JP2007031909A - Surface-sizing agent for papermaking and printing paper - Google Patents
Surface-sizing agent for papermaking and printing paper Download PDFInfo
- Publication number
- JP2007031909A JP2007031909A JP2005220139A JP2005220139A JP2007031909A JP 2007031909 A JP2007031909 A JP 2007031909A JP 2005220139 A JP2005220139 A JP 2005220139A JP 2005220139 A JP2005220139 A JP 2005220139A JP 2007031909 A JP2007031909 A JP 2007031909A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- sizing agent
- paper
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 47
- 238000007639 printing Methods 0.000 title claims abstract description 10
- -1 alkenyl ketene dimer Chemical compound 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000001384 succinic acid Substances 0.000 claims abstract description 20
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 13
- 150000003440 styrenes Chemical class 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 34
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000015278 beef Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000003760 tallow Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 229940114077 acrylic acid Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000123 paper Substances 0.000 description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000005476 size effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SPURMHFLEKVAAS-UHFFFAOYSA-N 1-docosene Chemical compound CCCCCCCCCCCCCCCCCCCCC=C SPURMHFLEKVAAS-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000002561 ketenes Chemical class 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical group CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
本発明は、製紙用表面サイズ剤（以下、表面サイズ剤と略すことがある）および印刷用紙に関する。 The present invention relates to a surface sizing agent for papermaking (hereinafter sometimes abbreviated as surface sizing agent) and printing paper.
表面サイズ剤は、一般には、例えばサイズプレスやゲートロールにより紙表面に直接塗工して用いられ、少ない固形分で紙に良好なサイズ効果を付与することができる。また、紙表面の細孔を塞いだり紙表面にフィルムを形成したりすることが可能であるため、各種溶剤に対するバリア適性やインクジェット適性、防滑適性などの各種特性を紙に付与することもできる。かかる表面サイズ剤としては、従来、アルキルまたはアルケニルケテンダイマーを用いたもの（例えば特許文献１）や、スチレン−マレイン酸共重合体（例えば特許文献２）等のアニオン性ポリマーを用いたものや、アルキルまたはアルケニルコハク酸中和塩を用いたもの（例えば特許文献３）が知られている。 The surface sizing agent is generally used by directly coating the surface of the paper with a size press or a gate roll, for example, and can impart a good sizing effect to the paper with a small solid content. In addition, since pores on the paper surface can be blocked or a film can be formed on the paper surface, various properties such as barrier suitability for various solvents, ink jet suitability, and slip resistance can be imparted to the paper. As such a surface sizing agent, conventionally, those using an alkyl or alkenyl ketene dimer (for example, Patent Document 1), those using an anionic polymer such as a styrene-maleic acid copolymer (for example, Patent Document 2), The thing using the alkyl or alkenyl succinic acid neutralization salt (for example, patent document 3) is known.
しかし、該アルキルまたはアルケニルケテンダイマーを用いる表面サイズ剤には、サイズ効果は良好であるが、紙の表面摩擦係数が著しく低下するためサイジングをした紙が高速回転の輪転機ですべりやすくなり、操業中止等のトラブルが発生しやすいという問題がある。また、該スチレン−マレイン酸共重合体による表面サイズ剤には、当該紙すべりの問題はほとんどないが、オフセット印刷時におけるいわゆるネッパリ（再湿粘着性）が強いという欠点がある。（「ネッパリ」とは、印刷時に供給される湿し水によって、表面サイズ剤を塗工した印刷用紙が強い粘着性を帯びてブランケット胴に張り付く現象をいい、ネッパリが強いと紙剥けによるブランケット胴等の汚れや印刷面の乱れや、ひどい場合には断紙による操業中止等の問題が生ずる。）また、アルキルまたはアルケニルコハク酸中和塩による表面サイズ剤を用いた場合には、当該ネッパリの点では良好ではあるが、本来的にサイズ効果が低いという問題がある。 However, the surface sizing agent using the alkyl or alkenyl ketene dimer has a good sizing effect, but the surface friction coefficient of the paper is remarkably lowered, so that the sized paper becomes slippery with a high-speed rotary press. There is a problem that troubles such as cancellation are likely to occur. Further, the surface sizing agent made of the styrene-maleic acid copolymer has almost no problem of paper slip, but has a drawback of so-called Nepari (rewetting adhesiveness) at the time of offset printing. ("Nepari" refers to the phenomenon that printing paper coated with a surface sizing agent is strongly sticky and sticks to the blanket cylinder by dampening water supplied during printing. If the surface sizing agent with alkyl or alkenyl succinic acid neutralized salt is used, the NEPPARI Although it is good in terms, there is a problem that the size effect is inherently low.
本発明は、前記従来の各表面サイズ剤の特長を活かした新規な表面サイズ剤を提供すること、すなわち、サイズ効果に優れるだけでなく、前記紙のすべりやネッパリという問題が生じないという、バランスのとれた表面サイジングを実現できる新規な表面サイズ剤を提供することを主な課題とする。 The present invention provides a novel surface sizing agent that takes advantage of the features of each of the conventional surface sizing agents, that is, not only is the size effect excellent, but also does not cause problems such as paper slipping and nepari. The main object is to provide a novel surface sizing agent capable of realizing excellent surface sizing.
本出願人は、アルキルまたはアルケニルケテンダイマーの優れたサイズ効果を得つつ、前記紙のすべりやネッパリを抑制できる表面サイジングにつき検討を重ねた。その結果、該アルキルまたはアルケニルケテンダイマーを利用した表面サイズ剤において、前記紙すべりの問題は紙表面の防滑性を高める作用を奏する特定のアニオン性ポリマーを併用することで解消でき、また該アニオン性ポリマーの利用に伴い生じやすい前記ネッパリの問題は、アルキルまたはアルケニルコハク酸中和塩を更に用いるることにより解消できることを見いだした。 The present applicant has repeatedly studied the surface sizing that can suppress slipping and nepari of the paper while obtaining the excellent size effect of the alkyl or alkenyl ketene dimer. As a result, in the surface sizing agent using the alkyl or alkenyl ketene dimer, the problem of the paper slip can be solved by using a specific anionic polymer having an action of enhancing the slip resistance of the paper surface, and the anionic property. It has been found that the Neppari problem that tends to occur with the use of a polymer can be solved by further using a neutralized alkyl or alkenyl succinic acid salt.
すなわち本発明は、アルキルまたはアルケニルケテンダイマー（Ａ）（以下、ケテンダイマー（Ａ）と略す）、α，β−不飽和カルボン酸類およびスチレン類を含有する不飽和単量体を重合させてなる水溶性共重合体（Ｂ）（以下、水溶性共重合体（Ｂ）と略す）、およびアルキルまたはアルケニルコハク酸中和塩（Ｃ）（以下、置換コハク酸中和塩（Ｃ）と略す）を含有する製紙用表面サイズ剤；該製紙用表面サイズ剤を紙表面に塗工してなる印刷用紙、に関する。 That is, the present invention provides an aqueous solution obtained by polymerizing an unsaturated monomer containing an alkyl or alkenyl ketene dimer (A) (hereinafter abbreviated as ketene dimer (A)), an α, β-unsaturated carboxylic acid and a styrene. Copolymer (B) (hereinafter abbreviated as water-soluble copolymer (B)) and alkyl or alkenyl succinic acid neutralized salt (C) (hereinafter abbreviated as substituted succinic acid neutralized salt (C)) The present invention relates to a paper surface sizing agent to be contained; a printing paper obtained by coating the paper surface sizing agent on the paper surface.
本発明の表面サイズ剤によれば、紙に優れたサイズ効果を付与できるだけでなく、前記紙すべりおよびネッパリの問題を好適に解決できるため、バランスのとれた表面サイジングが可能となる。 According to the surface sizing agent of the present invention, not only an excellent sizing effect can be imparted to paper, but also the problems of paper slip and Nepari can be suitably solved, and a balanced surface sizing becomes possible.
ケテンダイマー（Ａ）は、本発明の表面サイズ剤に、主として良好なサイズ効果を発現させるための必須成分である。具体的には、下記一般式（１）（式中、Ｒ1 およびＲ2 は同一でも異なっていてもよい、炭素数８〜３６程度（好ましくは１２〜３０程度、特に好ましくは１２〜２０）のアルキル基または炭素数８〜３６程度（好ましくは１２〜３０程度、特に好ましくは１２〜２０）のアルケニル基を示す。）で表されるものが好ましい。 The ketene dimer (A) is an essential component for causing the surface sizing agent of the present invention to mainly exhibit a good size effect. Specifically, the following general formula (1) (wherein R 1 and R 2 may be the same or different, and have about 8 to 36 carbon atoms (preferably about 12 to 30 and particularly preferably 12 to 20). Or an alkyl group having about 8 to 36 carbon atoms (preferably about 12 to 30 and particularly preferably about 12 to 20) is preferred.
当該化合物のＲ1 および／またはＲ2 の炭素数が８未満の場合には、疎水性が小さいので、本発明の所期の目的であるサイズ効果が得られ難くなる傾向にある。また、当該化合物のＲ1 および／またはＲ2 の炭素数が３６を越える場合には、サイズ効果が得られ難くなることは特にないが、商業上入手が困難となる。 When the number of carbon atoms of R 1 and / or R 2 of the compound is less than 8, the hydrophobicity is small, and the size effect that is the intended purpose of the present invention tends to be difficult to obtain. In addition, when the number of carbon atoms of R 1 and / or R 2 of the compound exceeds 36, the size effect is not particularly difficult to obtain, but it is difficult to obtain commercially.
炭素数８〜３６程度のアルキル基としては、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘニコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、トリアコンチル基、ドトリアコンチル基、トリトリアコンチル基、１−オクチル−２−デシル基、１−ヘキシル−２−オクチル基等が挙げられる。また、炭素数８〜３６程度のアルケニル基としては、かかる各種のアルキル基の内部に不飽和二重結合を有するアルケニル基が挙げられ、具体的には、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基、ヘニコセニル基、ドコセニル基、トリコセニル基、テトラコセニル基、ペンタコセニル基、ヘキサコセニル基、ヘプタコセニル基、オクタコセニル基、ノナコセニル基、トリアコンテニル基、ドトリアコンテニル基、トリトリアコンテニル基、１−オクチル−２−デセニル基、１−ヘキシル−２−オクテニル基等を例示できる。 As the alkyl group having about 8 to 36 carbon atoms, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group , Henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, dotriacontyl group, tritriacontyl group, 1-octyl-2-decyl group, 1-octyl And a hexyl-2-octyl group. Examples of the alkenyl group having about 8 to 36 carbon atoms include alkenyl groups having an unsaturated double bond inside such various alkyl groups. Specifically, octenyl group, nonenyl group, decenyl group, undecenyl group are exemplified. Group, dodecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, heptacocenyl group Nonacosenyl group, triacontenyl group, dotriacontenyl group, tritriacontenyl group, 1-octyl-2-decenyl group, 1-hexyl-2-octenyl group and the like can be exemplified.
該ケテンダイマー（Ａ）の具体例としては、例えばオクチル酸、カプリル酸、ノナン酸、デカン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、エイコサン酸、ベヘニン酸、セロチン酸、ヘントリアコンタン酸等の飽和一塩基酸から誘導されるアルキルケテンダイマー；オレイン酸、リノール酸、リノレン酸、エレオステアリン酸、アラキドン酸等の不飽和一塩基酸から誘導されるアルケニルケテンダイマー；ヤシ油、パーム油、オリーブ油、落花生油、菜種油、硬化牛脂油、ラード等の天然油脂から調製される天然油脂由来ケテンダイマー等が挙げられる。これらの中でもサイズ効果の観点より、ステアリン酸から誘導されたアルキルケテンダイマーおよび／または硬化牛脂油から調製された天然油脂由来ケテンダイマーが好ましい。これらは２種以上を組み合わせて用いることができる。 Specific examples of the ketene dimer (A) include, for example, octylic acid, caprylic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, serotic acid, hen Alkyl ketene dimers derived from saturated monobasic acids such as triacontanoic acid; Alkenyl ketene dimers derived from unsaturated monobasic acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid; coconut oil Natural oil-derived ketene dimers prepared from natural oils such as palm oil, olive oil, peanut oil, rapeseed oil, hydrogenated beef tallow oil, lard and the like. Among these, from the viewpoint of the size effect, an alkyl ketene dimer derived from stearic acid and / or a natural fat / oil-derived ketene dimer prepared from hydrogenated beef tallow oil is preferred. These can be used in combination of two or more.
なお、該ケテンダイマー（Ａ）は、水性分散液として用いるのが実用上好ましい。該水性分散液を調製する方法は特に制限されず、各種公知の手段を用いうる。例えば、高圧ホモジナイザー等を用いて一般式（１）で表される化合物を乳化する高圧乳化法や、各種公知の反転乳化法等を挙げることができる。また、乳化の際には、必要に応じて各種公知の乳化剤および／または保護コロイドを用いることもできる。なお、当該水性分散液中における前記一般式（１）で示される化合物の含有量は、通常１０〜３０重量％程度である。 In addition, it is practically preferable to use the ketene dimer (A) as an aqueous dispersion. The method for preparing the aqueous dispersion is not particularly limited, and various known means can be used. For example, a high-pressure emulsification method for emulsifying the compound represented by the general formula (1) using a high-pressure homogenizer or the like, various known inversion emulsification methods, and the like can be given. In emulsification, various known emulsifiers and / or protective colloids can be used as necessary. The content of the compound represented by the general formula (1) in the aqueous dispersion is usually about 10 to 30% by weight.
該乳化剤の具体例としては、例えばアルキル硫酸ソーダ、アルキルベンゼンスルホン酸ソーダ、ポリオキシエチレンアルキルエーテル硫酸ソーダ、ポリオキシエチレンアルキルフェニルエーテル硫酸ソーダ、アルキルスルホン酸ソーダ、ポリオキシエチレンアルキルエーテルスルホコハク酸ソーダ、ポリオキシエチレンアルキルエーテルリン酸エステル等のアニオン性乳化剤；ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、これらが有する末端水酸基をアセチル化してなる化合物等のノニオン性乳化剤等が挙げられ、これらは２種以上を組み合わせて用いることができる。なお、本発明の所期の効果を損なわない限りにおいて、各種公知のカチオン性界面活性剤を併用してもよい。 Specific examples of the emulsifier include, for example, sodium alkyl sulfate, sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkylphenyl ether sodium sulfate, alkyl sulfonic acid soda, polyoxyethylene alkyl ether sulfosuccinic acid soda, poly Anionic emulsifiers such as oxyethylene alkyl ether phosphates; nonionic emulsifiers such as polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, compounds formed by acetylating terminal hydroxyl groups of these, etc. These can be used in combination of two or more. Various known cationic surfactants may be used in combination as long as the desired effects of the present invention are not impaired.
該保護コロイドの具体例としては、例えばとうもろこし、ばれいしょ、タピオカ、小麦、コメ等の生澱粉を、希薄な水酸化ナトリウム溶液や次亜塩素酸ナトリウム等で処理してなる酸化澱粉；当該生澱粉に第１級、第２級、第３級のアミノ基や第４級アミンモニウ基からなる群より選ばれる少なくとも１種の塩基性窒素基を分子中に組み入れてなるカチオン化澱粉等のカチオン性保護コロイド；ナフタレンスルホン酸ナトリウムホルムアルデヒド縮合物、リグニンスルホン酸ナトリウムホルムアルデヒド縮合物等のアニオン性保護コロイド；ポリビニルアルコール等のノニオン性保護コロイド等が挙げられ、これらは２種以上を組み合わせて用いることができる。 Specific examples of the protective colloid include, for example, oxidized starch obtained by treating raw starch such as corn, potato, tapioca, wheat and rice with a dilute sodium hydroxide solution or sodium hypochlorite; Cationic protective colloids such as cationized starch comprising at least one basic nitrogen group selected from the group consisting of primary, secondary and tertiary amino groups and quaternary amine moniou groups in the molecule Anionic protective colloids such as sodium naphthalene sulfonate formaldehyde condensate and sodium lignin sulfonate formaldehyde condensate; nonionic protective colloids such as polyvinyl alcohol, and the like. These can be used in combination of two or more.
当該乳化剤および／または保護コロイドの使用量は、乳化効率等を考慮して、前記一般式（１）で示される化合物の重量に対して通常０．５〜１００重量％程度、好ましくは５〜３０重量％であるのがよい。 The amount of the emulsifier and / or protective colloid used is usually about 0.5 to 100% by weight, preferably 5 to 30% based on the weight of the compound represented by the general formula (1) in consideration of emulsification efficiency and the like. It should be weight percent.
水溶性共重合体（Ｂ）は、α，β−不飽和カルボン酸類およびスチレン類を含有する不飽和単量体（以下、不飽和単量体と略すことがある）を重合させてなるポリマーである。このものは、紙表面の防滑性を高める作用を奏することから、前記ケテンダイマー（Ａ）に起因して生じやすい前記紙すべりの問題を解消するために主に用いられる必須成分である。なお、水溶性共重合体（Ｂ）は、それ自体、サイズ効果を発現するものである。 The water-soluble copolymer (B) is a polymer obtained by polymerizing an unsaturated monomer (hereinafter sometimes abbreviated as an unsaturated monomer) containing α, β-unsaturated carboxylic acids and styrenes. is there. This is an essential component mainly used for solving the problem of paper slip that tends to occur due to the ketene dimer (A) because it has an effect of improving the slip resistance of the paper surface. Incidentally, the water-soluble copolymer (B) itself exhibits a size effect.
該不飽和単量体のうち、α，β−不飽和カルボン酸類としては、各種公知のものを特に限定なく使用することができる。具体的には、例えばアクリル酸、メタクリル酸等のα，β−不飽和モノカルボン酸類；無水マレイン酸、マレイン酸、クロトン酸、イタコン酸、フマル酸、ムコン酸、シトラコン酸等のα，β−不飽和ジカルボン酸類；当該α，β−不飽和ジカルボン酸類を、炭素数１〜１８程度のアルキル基（直鎖状、分岐鎖状、環状のいずれであってもよい）を有するアルコールとエステル結合させてなる、α，β−不飽和ジカルボン酸半エステル類；これらのうち遊離カルボキシル基を有するものを各種中和剤で中和してなる中和塩等を挙げることができ、これらは２種以上を併用することができる。 Among the unsaturated monomers, various known ones can be used without particular limitation as the α, β-unsaturated carboxylic acids. Specifically, α, β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; α, β- such as maleic anhydride, maleic acid, crotonic acid, itaconic acid, fumaric acid, muconic acid and citraconic acid Unsaturated dicarboxylic acids; The α, β-unsaturated dicarboxylic acids are ester-bonded with an alcohol having an alkyl group having about 1 to 18 carbon atoms (which may be linear, branched or cyclic). Α, β-unsaturated dicarboxylic acid half esters; neutralized salts obtained by neutralizing those having a free carboxyl group with various neutralizing agents, and the like. Can be used in combination.
なお、前記炭素数１〜１８程度のアルキル基の具体例としては、直鎖状のものとして、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ヘキシル基、デシル基、パルミチル基、ステアリル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基等が挙げられる。また、分岐鎖状のものとして、ｉ−プロピル基、ｉ−ブチル基、ｔ−ブチル基、ネオペンチル基、２−エチルヘキシル基等が挙げられる。また、環状のものとして、シクロヘキシル基、シクロペンチル基等が挙げられる。 In addition, specific examples of the alkyl group having about 1 to 18 carbon atoms include a straight chain, methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, decyl group, palmityl. Group, stearyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and the like. Examples of the branched chain include i-propyl group, i-butyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. Moreover, as a cyclic thing, a cyclohexyl group, a cyclopentyl group, etc. are mentioned.
また、前記中和剤としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；アンモニア、炭酸アンモニウム等のアンモニア類：モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、モノブチルアミン等の炭素数１〜１２程度の脂肪族アミン類；シクロヘキシルアミン等の脂環族アミン類；アニリン等の芳香族アミン類が挙げられ、これらは２種以上を併用することができる。これらの中でも、利便性の観点より、アンモニア類および／またはアルカリ金属水酸化物が好ましい。なお、前記α，β−不飽和カルボン酸類の中和率（％）、すなわち水溶性共重合体（Ｂ）に含まれるカルボキシル基の中和率（％）は、該水溶性共重合体（Ｂ）の水溶性を考慮して少なくとも通常５０％以上、より好ましくは８０〜１００％であるのがよい。また、前記中和の方法は特に限定されず、例えば未中和の前記α，β−不飽和カルボン酸類を用いて水溶性共重合体（Ｂ）を製造した後に、当該水溶性共重合体（Ｂ）が有するカルボキシル基を前記中和率の範囲で中和してもよいし、あるいは前記α，β−不飽和カルボン酸類を当該中和率の範囲で中和してなる中和塩を用いて水溶性共重合体（Ｂ）を製造してもよいし、これらの手段を組み合わせてもよい。 Examples of the neutralizing agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia such as ammonia and ammonium carbonate: monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, monobutylamine and the like. Aliphatic amines having about 1 to 12 carbon atoms; alicyclic amines such as cyclohexylamine; and aromatic amines such as aniline. These can be used in combination of two or more. Among these, ammonia and / or alkali metal hydroxide is preferable from the viewpoint of convenience. The neutralization rate (%) of the α, β-unsaturated carboxylic acids, that is, the neutralization rate (%) of the carboxyl group contained in the water-soluble copolymer (B) is determined by the water-soluble copolymer (B In consideration of water solubility, it is usually at least 50%, more preferably 80 to 100%. The neutralization method is not particularly limited. For example, after the water-soluble copolymer (B) is produced using the non-neutralized α, β-unsaturated carboxylic acids, the water-soluble copolymer (B The carboxyl group which B) has may be neutralized within the range of the neutralization rate, or a neutralized salt obtained by neutralizing the α, β-unsaturated carboxylic acids within the range of the neutralization rate is used. Thus, the water-soluble copolymer (B) may be produced, or these means may be combined.
前記不飽和単量体のうち、スチレン類としては、各種公知のものを特に限定なく使用することができる。具体的には、例えばスチレン、α−メチルスチレン、ｔ−ブチルスチレン、ジメチルスチレン、アセトキシスチレン、ヒドロキシスチレン、ビニルトルエン、クロルビニルトルエン、スチレンスルホン酸等が挙げられ、これらは２種以上を併用することができる。 Among the unsaturated monomers, various known styrenes can be used without any particular limitation. Specific examples include styrene, α-methyl styrene, t-butyl styrene, dimethyl styrene, acetoxy styrene, hydroxy styrene, vinyl toluene, chlorovinyl toluene, styrene sulfonic acid, and the like. be able to.
本発明では、前記不飽和単量体として、その他の各種不飽和単量体（以下、その他モノマー類という）を必要に応じて用いることができる。具体的には、例えば全体の炭素数が５〜２２程度のα−オレフィン類（以下、α−オレフィン類と略す）〔例えば、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン、１−エイコセン、１−ヘニコセン、１−ドコセン等の直鎖状α−オレフィン類；２，４，４−トリメチル−１−ペンテン（ジイソブチレン）、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン等の分岐状αオレフィン類、シクロヘキセン、メチルシクロヘキセン、ビニルシクロヘキサン、４−ビニルシクロヘキセン、シクロペンテン、メチルシクロペンテン等の環状α−オレフィン類等〕；前記炭素数１〜１８程度のアルキル基を置換基に有する(メタ)アクリル酸アルキルエステル類（以下（メタ）アクリル酸アルキルエステル類という）〔例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸Ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸Ｎ−オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸オクタデセニル、（メタ）アクリル酸イコシル、（メタ）アクリル酸ドコシル（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル等〕を用いることができる。（メタ）アクリル酸ヒドロキシアルキル類〔例えば（メタ）アクリル酸２−ヒドロキシメチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、グリセリンモノ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、（メタ）アリルアルコール等〕；アミド系不飽和単量体類〔例えば、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−ブチル（メタ）アクリルアミド、Ｎ−オクチル（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−プロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−２−ヒドロキシエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジヒドロキシエチル（メタ）アクリルミド、（メタ）アクリルアミドグリコール酸等〕；アミノアルキル系不飽和単量体類〔例えば、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸アミノブチル、（メタ）アクリル酸Ｎ−メチルアミノエチル、（メタ）アクリル酸Ｎ−メチルアミノプロピル、（メタ）アクリル酸Ｎ−メチルアミノブチル、（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノプロピル、（メタ）アクリル酸Ｎ，Ｎ−ジメチルアミノブチル、（メタ）アクリル酸Ｎ，Ｎ−ジエチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ−ジエチルアミノプロピル、（メタ）アクリル酸Ｎ，Ｎ−ジエチルアミノブチル等〕；ポリオキシアルキレン系不飽和単量体類〔例えば、ポリオキシアルキレン（メタ）アクリル酸エステル類、ポリオキシアルキレングリセリン（メタ）アクリル酸エステル類、ポリオキシアルキレンモノアルキル（メタ）アクリル酸エステル類、ポリオキシアルキレンモノアルケニル（メタ）アクリル酸エステル類、ポリオキシアルキレン（メタ）アリルエーテル、ポリオキシアルキレングリセリン（メタ）アリルエーテル等〕；スルホン酸系不飽和単量体類〔例えば、α−メチルスチレンスルホン酸、ビニルスルホン酸、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸、（メタ）アリルアミド−Ｎ−メチルスルホン酸、（メタ）アクリルアミドフェニルプロパンスルホン酸、（メタ）アリルスルホン酸、（メタ）アクリル酸スルホエチル、（メタ）アクリル酸スルホプロピル、（メタ）アクリル酸スルホ２−ヒドロキシプロピル等〕；硫酸エステル系不飽和単量体類〔例えば、（メタ）アクリル酸ヒドロキシエチルの硫酸エステル、（メタ）アクリル酸ヒドロキシプロピル硫酸エステル、（メタ）アクリル酸ポリオキシアルキレン硫酸エステル、硫酸（メタ）アリルエステル、アリロキシポリオキシアルキレン硫酸エステル等〕；ビニルエステル系単量体類〔例えば、プロピオン酸ビニル、酢酸ビニル等〕；（メタ）アクリルニトリル等のニトリル系単量体類等が挙げられ、これらは２種以上を組み合わせて用いることができる。 In the present invention, as the unsaturated monomer, other various unsaturated monomers (hereinafter referred to as other monomers) can be used as necessary. Specifically, for example, α-olefins having a total carbon number of about 5 to 22 (hereinafter abbreviated as α-olefins) [for example, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene Linear α-olefins such as 1-docosene; 2,4,4-trimethyl-1-pentene (diisobutylene), 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- Branched α-olefins such as 1-pentene, cyclohexene, methylcyclohexene, vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, Cyclic α-olefins such as lucyclopentene, etc.]; (meth) acrylic acid alkyl esters (hereinafter referred to as (meth) acrylic acid alkyl esters) having an alkyl group having about 1 to 18 carbon atoms as a substituent [for example, Methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meta ) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, octadecenyl (meth) acrylate , Icosyl (meth) acrylate, docosyl (meth) acrylate (meth) acrylic acid Kuropenchiru, can be used (meth) cyclohexyl acrylate, etc.]. Hydroxyalkyl (meth) acrylate [for example, 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) allyl alcohol, etc.]; amide unsaturated monomers [e.g., (meth) acrylamide, N-methylol (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N- Octyl (meta) aqua Luamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N , N-dihydroxyethyl (meth) acrylimide, (meth) acrylamide glycolic acid, etc.]; aminoalkyl unsaturated monomers [for example, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, (meth ) Aminobutyl acrylate, N-methylaminoethyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N-methylaminobutyl (meth) acrylate, N, N-dimethylamino (meth) acrylate Ethyl N, N-dimethyl (meth) acrylate Minopropyl, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate Etc.]; polyoxyalkylene unsaturated monomers [for example, polyoxyalkylene (meth) acrylic acid esters, polyoxyalkylene glycerin (meth) acrylic acid esters, polyoxyalkylene monoalkyl (meth) acrylic acid esters , Polyoxyalkylene monoalkenyl (meth) acrylic acid esters, polyoxyalkylene (meth) allyl ether, polyoxyalkylene glycerin (meth) allyl ether, etc.]; sulfonic acid unsaturated monomers [for example, α- Methyl styrene sulfonic acid, vinyl Sulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) allylamide-N-methylsulfonic acid, (meth) acrylamide phenylpropanesulfonic acid, (meth) allylsulfonic acid, sulfoethyl (meth) acrylate , (Meth) acrylic acid sulfopropyl, (meth) acrylic acid sulfo 2-hydroxypropyl and the like]; sulfate ester unsaturated monomers [for example, sulfate of hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxypropyl sulfate, (meth) acrylic acid polyoxyalkylene sulfate, sulfate (meth) allyl ester, allyloxy polyoxyalkylene sulfate, etc.]; vinyl ester monomers [eg, vinyl propionate, vinyl acetate, etc. ] (Meth) acrylic nitrite Nitrile monomers such as Le, and the like. These may be used in combination of two or more.
該その他モノマー類の中でも、ネッパリの抑制とサイズ効果の向上の点で優れることから、前記α−オレフィン類が好ましい。特に、ネッパリ抑制の観点からは炭素数１４〜１８のα−オレフィン類が、またサイズ効果の観点からは２，４，４−トリメチル−１−ペンテンが好ましい。また、紙表面の防滑性が高まり前記紙すべりを抑制しやすくなることから、前記（メタ）アクリル酸アルキルエステル類が好ましく、特に炭素数１〜６のアルキル基を有する（メタ）アクリル酸アルキルエステル類が好ましい。該α−オレフィン類と（メタ）アクリル酸アルキルエステル類は同時に用いてもよい。 Among these other monomers, the α-olefins are preferred because they are excellent in suppressing Nepari and improving the size effect. In particular, α-olefins having 14 to 18 carbon atoms are preferable from the viewpoint of Nepari suppression, and 2,4,4-trimethyl-1-pentene is preferable from the viewpoint of size effect. Further, the (meth) acrylic acid alkyl esters are preferred, and the (meth) acrylic acid alkyl esters having an alkyl group having 1 to 6 carbon atoms are preferred because the paper surface has an increased anti-slip property and can easily suppress the paper slip. Are preferred. The α-olefins and (meth) acrylic acid alkyl esters may be used simultaneously.
該不飽和単量体を構成する各種単量体の使用重量％は特に限定されないが、本発明の所期の効果を考慮して、該α，β−不飽和カルボン酸類が２０〜８０重量％程度（好ましくは２５〜７５重量％程度、より好ましくは３５〜６５重量％）、該スチレン類が８０〜２０重量％程度（好ましくは７５〜２５重量％程度、より好ましくは６５〜３５重量％）、該その他モノマー類が０〜１０重量％程度（好ましくは０〜５重量％）であるのが好ましい。該α，β−不飽和カルボン酸類の使用重量％が２０重量％に満たない場合には、前記水溶性共重合体（Ｂ）が水溶化し難くなるため、例えば水溶性共重合体（Ｂ）を後述する乳化重合により製造する場合において、反応系内に凝集物が発生しやすくなる傾向にある。また、該α，β−不飽和カルボン酸類の含有量が８０重量％を超える場合には、水溶性共重合体（Ｂ）の親水性が高くなりすぎるため、本発明の所期の目的であるサイズ効果が得られ難くなる傾向にある。なお、その他モノマー類の使用量が１０重量％を超える場合には、前記紙の表面摩擦係数の低下を抑制するという本発明の所期の効果（防滑効果）が得られ難くなる傾向にある。 The use weight% of various monomers constituting the unsaturated monomer is not particularly limited, but the α, β-unsaturated carboxylic acid is 20 to 80 weight% in consideration of the intended effect of the present invention. About (preferably about 25 to 75% by weight, more preferably about 35 to 65% by weight), and about 80 to 20% by weight of the styrenes (preferably about 75 to 25% by weight, more preferably about 65 to 35% by weight) The other monomers are preferably about 0 to 10% by weight (preferably 0 to 5% by weight). When the used weight% of the α, β-unsaturated carboxylic acid is less than 20% by weight, the water-soluble copolymer (B) is difficult to be water-soluble. For example, the water-soluble copolymer (B) In the case of producing by emulsion polymerization described later, aggregates tend to be generated in the reaction system. In addition, when the content of the α, β-unsaturated carboxylic acid exceeds 80% by weight, the hydrophilicity of the water-soluble copolymer (B) becomes too high, which is an intended object of the present invention. It tends to be difficult to obtain a size effect. In addition, when the usage-amount of other monomers exceeds 10 weight%, it exists in the tendency for the effect (antislip effect) of this invention of suppressing the fall of the surface friction coefficient of the said paper to become difficult to be acquired.
水溶性共重合体（Ｂ）を製造する方法は特に限定されず、各種公知の共重合反応を利用できる。例えば、適当な反応容器に前記不飽和単量体を所定量づつ仕込み、次いで溶媒として水（例えば軟水など）および／または各種有機溶剤を仕込み、更に公知の重合開始剤や必要に応じて公知の連鎖移動剤を仕込んだ後、攪拌下に反応系を２０〜１４０℃程度に昇温し、次いで同温度範囲で２〜１２時間程度かけて重合反応を行い、その後必要に応じて前記段落〔００２１〕で例示した中和剤を用いて中和処理を行うことにより、該水溶性共重合体（Ｂ）を製造することができる。なお、反応系は窒素雰囲気とするのが好ましい。 The method for producing the water-soluble copolymer (B) is not particularly limited, and various known copolymerization reactions can be used. For example, a predetermined amount of the unsaturated monomer is charged into a suitable reaction vessel, and then water (for example, soft water) and / or various organic solvents are charged as a solvent. Further, a known polymerization initiator or a known one as required. After the chain transfer agent is charged, the reaction system is heated to about 20 to 140 ° C. with stirring, and then the polymerization reaction is carried out in the same temperature range for about 2 to 12 hours. The water-soluble copolymer (B) can be produced by performing neutralization using the neutralizing agent exemplified in the above. The reaction system is preferably a nitrogen atmosphere.
前記有機溶剤としては、各種公知のものを特に限定なく使用することができる。具体的には、例えばエチルアルコール、イソプロピルアルコール等の低級アルコール類；ベンゼン、トルエン等の芳香族炭化水素類；アセトン、メチルエチルケトン等の低級ケトン類；酢酸エチル、クロロホルム、ジメチルホルムアミド等が挙げられ、これらは２種以上を組み合わせて用いることができる。なお、環境負荷や作業衛生を考慮すれば、これらの有機溶剤は最終的には反応系から減圧蒸留等の各種公知の手段によりできるだけ留去しておくのが好ましい。 As the organic solvent, various known solvents can be used without any particular limitation. Specific examples include lower alcohols such as ethyl alcohol and isopropyl alcohol; aromatic hydrocarbons such as benzene and toluene; lower ketones such as acetone and methyl ethyl ketone; ethyl acetate, chloroform and dimethylformamide. Can be used in combination of two or more. In consideration of environmental load and occupational hygiene, it is preferable to finally remove these organic solvents from the reaction system as much as possible by various known means such as vacuum distillation.
前記重合開始剤としては、各種公知のものを特に限定なく使用することができる。具体的には、例えば過酸化水素、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物；ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等の有機過酸化物；２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレイト等のアゾ系化合物等が挙げられ、これらは２種以上を組み合わせて用いることができる。なお、重合開始剤が無機過酸化物や有機過酸化物の場合には、各種公知の還元剤（例えば、亜硫酸ナトリウム、チオ硫酸ナトリウム等）を併用することによって、反応系をレドックス系にすることもできる。なお該重合開始剤の使用量は、前記不飽和単量体の総重量に対して通常０．０１〜５重量％程度である。 As the polymerization initiator, various known ones can be used without particular limitation. Specifically, for example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; organic peroxides such as benzoyl peroxide, dicumyl peroxide, and lauryl peroxide; 2,2′-azobisiso Examples thereof include azo compounds such as butyronitrile and dimethyl-2,2′-azobisisobutyrate, and these can be used in combination of two or more. When the polymerization initiator is an inorganic peroxide or an organic peroxide, the reaction system is made redox by using various known reducing agents (for example, sodium sulfite, sodium thiosulfate, etc.) in combination. You can also. In addition, the usage-amount of this polymerization initiator is about 0.01 to 5 weight% normally with respect to the total weight of the said unsaturated monomer.
前記連鎖移動剤としては、各種公知のものを特に限定なく使用することができる。具体的には、例えばｎ−ドデシルメルカプタン、ｎ−オクチルメルカプタン、ターシャリードデシルメルカプタン、ｎ−オクタデシルメルカプタン、ｎ−ヘキサデシルメルカプタン等のアルキルメルカプタン系連鎖移動剤、ならびに２−メルカプトベンゾチアゾール、ブロムトリクロルメタン、アルファ−メチルスチレンダイマ−等が挙げられ、これらは２種以上を組み合わせて用いることができる。なお該連鎖移動剤の使用量は、前記不飽和単量体の総重量に対して通常０〜５重量％程度である。 As the chain transfer agent, various known ones can be used without particular limitation. Specifically, for example, alkyl mercaptan chain transfer agents such as n-dodecyl mercaptan, n-octyl mercaptan, tertiary decyl mercaptan, n-octadecyl mercaptan, n-hexadecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane , Alpha-methylstyrene dimer, and the like, which can be used in combination of two or more. In addition, the usage-amount of this chain transfer agent is about 0 to 5 weight% normally with respect to the total weight of the said unsaturated monomer.
以上の方法により、水溶液状の水溶性共重合体（Ｂ）を得ることができる。該水溶性共重合体（Ｂ）の重量平均分子量は通常１０００〜１０００００程度であるが、特に前記紙すべりの抑制の観点より５０００〜５００００であるのが好ましい。重量平均分子量が１０００未満であると前記サイズ効果が十分でなくなる傾向にあり、一方、１０００００を超えると紙へ表面サイズ剤を塗工する際にハンドリング性が低下する傾向にある。 By the above method, an aqueous water-soluble copolymer (B) can be obtained. The water-soluble copolymer (B) usually has a weight average molecular weight of about 1,000 to 100,000, but is preferably 5,000 to 50,000 from the viewpoint of suppressing the paper slip. When the weight average molecular weight is less than 1000, the size effect tends to be insufficient. On the other hand, when the weight average molecular weight exceeds 100,000, the handling property tends to be lowered when a surface sizing agent is applied to paper.
なお、水溶性共重合体（Ｂ）は、通常固形分濃度１０〜３０重量％において、１０〜１００００ｍＰａ・ｓ（２５℃）程度の粘度、また８．０〜９．５程度のｐＨに調整するのが実用上好ましい。 The water-soluble copolymer (B) is usually adjusted to a viscosity of about 10 to 10000 mPa · s (25 ° C.) and a pH of about 8.0 to 9.5 at a solid content concentration of 10 to 30% by weight. Is practically preferable.
置換コハク酸中和塩（Ｃ）は、前記水溶性共重合体（Ｂ）の利用に伴い生じやすい前記ネッパリの問題を解消するために用いる必須成分である。具体的には、炭素数８〜３６程度（好ましくは１２〜３０程度、特に好ましくは１２〜２０）のアルキル基または同炭素数のアルケニル基で置換された（無水）マレイン酸（以下、アルキルまたはアルケニルコハク酸（無水物）という）を、前記中和剤で中和してなる中和塩化合物である。 The substituted succinic acid neutralized salt (C) is an essential component used to solve the Nepari problem that is likely to occur with the use of the water-soluble copolymer (B). Specifically, (anhydrous) maleic acid (hereinafter, alkyl or alkyl) having about 8 to 36 carbon atoms (preferably about 12 to 30 carbon atoms, particularly preferably about 12 to 20 carbon atoms) or an alkenyl group having the same carbon number. This is a neutralized salt compound obtained by neutralizing alkenyl succinic acid (anhydride) with the neutralizing agent.
ここに、該炭素数８〜３６程度のアルキル基および／または該炭素数８〜３６程度のアルケニル基とは、前記段落〔００２１〕で例示したものと同様である。これらの炭素数が８未満の場合には、表面サイジングにおいて前記ネッパリが発生しやすくなる傾向にあり、また３６より大きいと、前記置換コハク酸の中和が困難となり置換コハク酸中和塩（Ｃ）自体が得られ難くなる傾向にある。また、該中和剤は、前記段落〔００２１〕で例示したものと同様である（利便性の観点より、アンモニア類および／またはアルカリ金属水酸化物が好ましい）。 Here, the alkyl group having about 8 to 36 carbon atoms and / or the alkenyl group having about 8 to 36 carbon atoms are the same as those exemplified in the paragraph [0021]. When the number of carbon atoms is less than 8, the Nepari tends to be easily generated in the surface sizing. When the number is more than 36, neutralization of the substituted succinic acid becomes difficult and the substituted succinic acid neutralized salt (C ) Tends to be difficult to obtain. The neutralizing agent is the same as that exemplified in the paragraph [0021] (from the viewpoint of convenience, ammonia and / or alkali metal hydroxide is preferable).
なお、前記アルキルまたはアルケニルコハク酸（無水物）は、一般的には、炭素数８〜３６程度のオレフィン類に（無水）マレイン酸を付加反応させることにより得ることができる。特に、サイズ効果の観点より、該オレフィン類としては、二重結合が２位以内の内部に存在する炭素数８〜３６程度の内部オレフィン類が好ましい。 The alkyl or alkenyl succinic acid (anhydride) can be generally obtained by addition reaction of (anhydrous) maleic acid with an olefin having about 8 to 36 carbon atoms. In particular, from the viewpoint of the size effect, the olefin is preferably an internal olefin having about 8 to 36 carbon atoms in which a double bond is present within the 2-position.
かかる置換コハク酸中和塩（Ｃ）としては、入手容易性の観点より、オクタデシル基を有する無水コハク酸中和塩（特にナトリウム塩）が好ましい。該置換コハク酸中和塩（Ｃ）は２種以上を用いることができる。 As the substituted succinic acid neutralized salt (C), a succinic anhydride neutralized salt having an octadecyl group (particularly a sodium salt) is preferable from the viewpoint of availability. Two or more kinds of the substituted succinic acid neutralized salt (C) can be used.
本発明の表面サイズ剤は、前記ケテンダイマー（Ａ）、水溶性共重合体（Ｂ）、置換コハク酸中和塩（Ｃ）を各種公知の手段で混合してなるものであり、混合手段は特に限定されない。例えば、これらを各種公知の混合機具で一度に混合することはもちろんのこと、水溶性共重合体（Ｂ）および置換コハク酸中和塩（Ｃ）を混合したものにケテンダイマー（Ａ）を添加したり、水溶性共重合体（Ｂ）を製造している最中にケテンダイマー（Ａ）および置換コハク酸中和塩（Ｃ）を反応系に添加してもよい。また、混合の時期も特に制限されず、サイジングの直前にこれらを混合してもよい。 The surface sizing agent of the present invention is obtained by mixing the ketene dimer (A), the water-soluble copolymer (B), and the substituted succinic acid neutralized salt (C) by various known means. There is no particular limitation. For example, ketene dimer (A) is added to a mixture of water-soluble copolymer (B) and substituted succinic acid neutralization salt (C) as well as mixing them at once with various known mixing devices. Alternatively, during the production of the water-soluble copolymer (B), the ketene dimer (A) and the substituted succinic acid neutralized salt (C) may be added to the reaction system. Further, the timing of mixing is not particularly limited, and these may be mixed immediately before sizing.
なお、本発明の表面サイズ剤における前記ケテンダイマー（Ａ）、水溶性共重合体（Ｂ）、置換コハク酸中和塩（Ｃ）の各使用重量は、本発明の所期の効果を考慮して、ケテンダイマー（Ａ）と水溶性共重合体（Ｂ）の固形分重量比〔（Ａ）／（Ｂ）〕が０．２５〜４．０程度（好ましくは１．０〜３．０）、（Ａ）と（Ｃ）の固形分重量比〔（Ａ）／（Ｃ）〕が０．２５〜４．０（好ましくは１．０〜２．０）であるのがよい。かかる数値範囲を逸脱すると、紙へのサイズ効果付与と、前記紙すべりおよびネッパリの抑制のバランスが損なわれる傾向にある。 In addition, each use weight of the said ketene dimer (A), water-soluble copolymer (B), and substituted succinic acid neutralized salt (C) in the surface sizing agent of the present invention takes into account the intended effect of the present invention. The solids weight ratio [(A) / (B)] of the ketene dimer (A) and the water-soluble copolymer (B) is about 0.25 to 4.0 (preferably 1.0 to 3.0). The weight ratio [(A) / (C)] of (A) and (C) should be 0.25 to 4.0 (preferably 1.0 to 2.0). When deviating from such a numerical range, the balance between imparting the size effect to the paper and the suppression of the paper slip and Nepari tends to be impaired.
こうして得られる表面サイズ剤は、通常黄単色の透明状の外観を有しており、固形分濃度２０重量％において、通常１０〜５０００ｍＰａ・ｓ（２５℃）程度の粘度を有し、７．０〜８．０程度のｐＨを有する。 The surface sizing agent thus obtained usually has a yellow solid transparent appearance, and has a viscosity of usually about 10 to 5000 mPa · s (25 ° C.) at a solid content concentration of 20% by weight, and 7.0. It has a pH of about 8.0.
なお、本発明の表面サイズ剤には、必要に応じて各種公知の添加剤を加えてもよい。具体的には、例えば前記各種澱粉類や酵素変性澱粉、カルボキシメチルセルロース等のセルロース類、ポリビニルアルコール類、ポリアクリルアミド類、アルギン酸ソーダ等の水溶性高分子等の紙力増強剤；各種公知のネッパリ防止剤、防滑剤、防腐剤、防錆剤、ｐＨ調整剤、消泡剤、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤、顔料、染料；各種公知のサイズ剤、エマルジョン型サイズ剤を添加することができる。 In addition, you may add various well-known additives to the surface sizing agent of this invention as needed. Specifically, for example, the above-mentioned various starches, enzyme-modified starches, celluloses such as carboxymethylcellulose, paper strength enhancers such as water-soluble polymers such as polyvinyl alcohols, polyacrylamides and sodium alginate; Agent, anti-slip agent, antiseptic agent, rust preventive agent, pH adjuster, antifoaming agent, thickener, filler, antioxidant, water resistance agent, film-forming aid, pigment, dye; various known sizing agents, An emulsion type sizing agent can be added.
本発明の印刷用紙は、前記表面サイズ剤を各種の紙に各種公知の手段で塗工したものである。紙の種類は特に制限されず、具体的には、例えばフォーム用紙、ＰＰＣ用紙、感熱記録原紙、感圧記録原紙等の記録用紙およびその原紙、アート紙、キャストコート紙、上質コート紙等のコート紙用の原紙、クラフト紙、純白ロール紙等の包装用紙、その他、ノート用紙、書籍用紙、印刷用紙、新聞用紙等の各種紙（洋紙）、マニラボール、白ボール、チップボール等の紙器用板紙およびライナー等の板紙が挙げられる。 The printing paper of the present invention is obtained by applying the surface sizing agent to various papers by various known means. The type of paper is not particularly limited, and specifically, for example, recording paper such as foam paper, PPC paper, thermal recording base paper, pressure-sensitive recording base paper and the base paper, art paper, cast coated paper, high quality coated paper, etc. Paper base paper, kraft paper, wrapping paper such as pure white roll paper, and other paper (paper) such as notebook paper, book paper, printing paper, and newsprint paper, paperboard for paper containers such as Manila ball, white ball, chip ball, etc. And board such as a liner.
また、塗工手段も特に限定されず、具体的には、例えば含浸法、サイズプレス法、ゲートロール法、バーコーター法、カレンダー法、スプレー法等を利用することができる。塗工方法としては、例えば含浸法、サイズプレス法、ゲートロール法、バーコーター法、カレンダー法、スプレー法を採用できる。なお、本発明の表面サイズ剤によれば前記紙すべりが生じにくくなるので、本発明の印刷用紙はブランケット胴が高速で回転する前記サイズプレス法やゲートロール法が好ましく利用される。なお、本発明の表面サイズ剤の紙への塗工量は特に限定されないが、通常は０．００１〜２ｇ（固形分）／ｍ2、好ましくは０．００５〜０．５ｇ（固形分）／ｍ2 程度である。 The coating means is not particularly limited, and specifically, for example, an impregnation method, a size press method, a gate roll method, a bar coater method, a calendar method, a spray method, or the like can be used. As the coating method, for example, an impregnation method, a size press method, a gate roll method, a bar coater method, a calendar method, and a spray method can be employed. The surface sizing agent of the present invention makes it difficult for the paper slip to occur. Therefore, the size press method and the gate roll method in which the blanket cylinder rotates at high speed are preferably used for the printing paper of the present invention. The amount of the surface sizing agent of the present invention applied to the paper is not particularly limited, but is usually 0.001 to 2 g (solid content) / m 2 , preferably 0.005 to 0.5 g (solid content) / m is 2.
以下、実施例、比較例、参照例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお各例中、部とは特記しない限りすべて重量基準である。 EXAMPLES Hereinafter, although an Example, a comparative example, and a reference example are given and this invention is demonstrated concretely, this invention is not limited to these. In each example, parts are based on weight unless otherwise specified.
調製例１（ケテンダイマー（Ａ）の調製）
フラスコに、硬化牛脂油から調製されたアルキルケテンダイマー（前記一般式（１）において、Ｒ１とＲ２が炭素数１４〜１６の範囲にある直鎖アルキル基であるもの）１８部、とうもろこし由来のカチオン化澱粉（窒素含有率０．５％以上）を蒸し煮して得られた１０％水溶液４２．８部、ならびに脱イオン水４８部を仕込み、系を７０〜８０℃に加熱し、ホモミキサーで予備分散させた後、同温度にて３００ｋｇ／ｃｍ2の条件下にホモジナイザーに２回通して強制分散させ、じかに冷却し、固形分濃度が２０．５％、粘度１５ｍＰａ・ｓのケテンダイマー（Ａ−１）の水性分散液を得た。
Preparation Example 1 (Preparation of ketene dimer (A))
In the flask, 18 parts of alkyl ketene dimer prepared from hydrogenated beef tallow oil (in the general formula (1), R 1 and R 2 are linear alkyl groups having a carbon number of 14 to 16), derived from corn 42.8 parts of a 10% aqueous solution obtained by steaming a cationized starch (nitrogen content of 0.5% or more) and 48 parts of deionized water were added, and the system was heated to 70-80 ° C. Pre-dispersed with a mixer, then forcedly dispersed twice through a homogenizer under the same temperature at 300 kg / cm 2 , cooled directly, and a ketene dimer with a solid content concentration of 20.5% and a viscosity of 15 mPa · s An aqueous dispersion of (A-1) was obtained.
調製例２（ケテンダイマー（Ａ）の調製）
調製例１で用いたアルケルケテンダイマーを、ステアリン酸から誘導された飽和アルキルケテンダイマーに代えた以外は同様にして、固形分濃度が２０．５％、粘度１６ｍＰａ・ｓのケテンダイマー（Ａ−２）の水性分散液を得た。
Preparation Example 2 (Preparation of ketene dimer (A))
A ketene dimer (A-2) having a solid content concentration of 20.5% and a viscosity of 16 mPa · s was used except that the alkelketene dimer used in Preparation Example 1 was replaced with a saturated alkyl ketene dimer derived from stearic acid. ) Aqueous dispersion was obtained.
調製例３（水溶性共重合体（Ｂ）の製造）
攪拌器、還流冷却管、窒素導入管付きの反応器に窒素を導入しながらマレイン酸のイソブチルアルコール半エステル６８．８部、マレイン酸５８．８部およびトルエン１５０部を仕込み、窒素気流下に攪拌しながら反応系を１１０℃まで昇温した。次いで、滴下ロートにスチレン１０４部、また別の滴下ロートにｔ-ブチルパーオキシベンゾエート５．８部およびトルエン３５部を仕込み、これらの滴下ロートから約１．５時間を要してそれぞれを容器内に滴下し、還流下に約２時間保温した。その後、ｔ−ブチルパーオキシベンゾエート２．３部およびトルエン１５部を約３０分要して滴下し、更に同温度で１時間保温した。減圧下にトルエンを留去し、重合物を水酸化ナトリウム１２．８部、所定量の水および２８％アンモニア水８１．６部で中和することにより スチレン−マレイン酸共重合体水溶液（Ｂ−１）を得た。このものの固形分濃度は２０．０％、ｐＨは９．３、２５℃における粘度は１００ｍＰａ・ｓであった。
Preparation Example 3 (Production of water-soluble copolymer (B))
While introducing nitrogen into a reactor equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 68.8 parts of maleic acid isobutyl alcohol half ester, 58.8 parts of maleic acid and 150 parts of toluene were charged and stirred under a nitrogen stream. While raising the temperature of the reaction system to 110 ° C. Next, 104 parts of styrene was charged into the dropping funnel, and 5.8 parts of t-butyl peroxybenzoate and 35 parts of toluene were charged into another dropping funnel, and about 1.5 hours were required from these dropping funnels. The mixture was added dropwise to the solution and kept warm under reflux for about 2 hours. Thereafter, 2.3 parts of t-butyl peroxybenzoate and 15 parts of toluene were dropped over about 30 minutes, and the mixture was further kept at the same temperature for 1 hour. Toluene was distilled off under reduced pressure, and the polymer was neutralized with 12.8 parts of sodium hydroxide, a predetermined amount of water and 81.6 parts of 28% aqueous ammonia, to give a styrene-maleic acid copolymer aqueous solution (B- 1) was obtained. This had a solid content concentration of 20.0%, a pH of 9.3, and a viscosity at 25 ° C. of 100 mPa · s.
調製例４（水溶性共重合体（Ｂ）の製造）
調製例１と同様の反応容器に窒素を導入しながらマレイン酸９８部およびトルエン７５．２部を仕込み、窒素気流下に攪拌しながら反応系を１１０℃まで昇温した。次いで、滴下ロートにスチレン９３．６部、ジイソブチレン（２，２，４−トリメチル−１−ペンテンの含有率７６％）８．８部、１−ヘキサデセン９．０部を仕込み、また別の滴下ロートにｔ-ブチルパーオキシベンゾエート５．２部およびトルエン３５部を仕込み、これらの滴下ロートから約１．５時間を要してそれぞれを容器内に滴下し、還流下に約２時間保温した。その後、ｔ−ブチルパーオキシベンゾエート２．１部およびトルエン１５部を約３０分要して滴下し、更に同温度で１時間保温した。減圧下にトルエンを留去し、重合物を水酸化ナトリウム１６部、所定量の水および２８％アンモニア水９７部で中和することにより水溶液状の水溶性共重合体（Ｂ−２）を得た。このものの固形分濃度は２０．０％、ｐＨは８．７、２５℃における粘度は８０ｍＰａ・ｓであった。
Preparation Example 4 (Production of water-soluble copolymer (B))
While introducing nitrogen into the same reaction vessel as in Preparation Example 1, 98 parts of maleic acid and 75.2 parts of toluene were charged, and the reaction system was heated to 110 ° C. while stirring under a nitrogen stream. Next, 93.6 parts of styrene, 8.8 parts of diisobutylene (76% content of 2,2,4-trimethyl-1-pentene) and 9.0 parts of 1-hexadecene were charged into the dropping funnel. A funnel was charged with 5.2 parts of t-butyl peroxybenzoate and 35 parts of toluene, and each of these dropping funnels was added dropwise to the vessel in about 1.5 hours, and kept warm for about 2 hours under reflux. Thereafter, 2.1 parts of t-butyl peroxybenzoate and 15 parts of toluene were added dropwise over about 30 minutes, and the mixture was further kept at the same temperature for 1 hour. Toluene was distilled off under reduced pressure, and the polymer was neutralized with 16 parts of sodium hydroxide, a predetermined amount of water and 97 parts of 28% aqueous ammonia to obtain an aqueous solution (B-2) in the form of an aqueous solution. It was. This had a solid content concentration of 20.0%, a pH of 8.7, and a viscosity at 25 ° C. of 80 mPa · s.
調製例５（水溶性共重合体（Ｂ）の合成）
攪拌器、還流冷却管、窒素導入管付きの反応容器に、窒素気流下に軟水１００部およびイソプロピルアルコール７５部を仕込み、攪拌しながら系を加熱して８０℃まで昇温した。次いで反応容器にアクリル酸５５部とスチレン４５部を混合した溶液と、過硫酸カリウム５部を水１２０部に溶解した重合開始剤水溶液をそれぞれ約３時間かけて系内に滴下した。その後系を２時間保温して反応を完結させた。次いでイソプロピルアルコールを留去し、冷却後２８％アンモニア水溶液４６．４部を加え、更に水で希釈して固形分濃度が重量％になるように調整し、２５℃の粘度が１１００ｍＰａ・ｓである水溶性共重合体（Ｂ−３）を得た。
Preparation Example 5 (Synthesis of water-soluble copolymer (B))
A reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with 100 parts of soft water and 75 parts of isopropyl alcohol under a nitrogen stream, and the system was heated to 80 ° C. while stirring. Next, a solution obtained by mixing 55 parts of acrylic acid and 45 parts of styrene in a reaction vessel and an aqueous polymerization initiator solution obtained by dissolving 5 parts of potassium persulfate in 120 parts of water were dropped into the system over about 3 hours. The system was then kept warm for 2 hours to complete the reaction. Next, isopropyl alcohol is distilled off, and after cooling, 46.4 parts of 28% aqueous ammonia solution is added, and further diluted with water to adjust the solid content concentration to wt%, and the viscosity at 25 ° C. is 1100 mPa · s. A water-soluble copolymer (B-3) was obtained.
調製例６（置換コハク酸中和塩（Ｃ）の調製）
冷却管、撹拌機の付いたフラスコに、炭素数が１４でありかつ５位以内の位置に二重結合を有する内部オレフィンに無水マレイン酸を付加して得たアルケニルコハク酸無水物１００部を仕込み、次いで水酸化カリウム３３．６部を水２１０部に溶解した溶液を加えて系を８０〜９０℃に加温し、該酸無水物を溶解した後冷却し、更に水で希釈して、固形分重量が３５％の置換コハク酸中和塩（Ｃ−１）を得た。
Preparation Example 6 (Preparation of Substituted Succinic Acid Neutralized Salt (C))
A flask equipped with a condenser and a stirrer was charged with 100 parts of alkenyl succinic anhydride obtained by adding maleic anhydride to an internal olefin having 14 carbon atoms and a double bond at a position within 5 position. Then, a solution prepared by dissolving 33.6 parts of potassium hydroxide in 210 parts of water was added, and the system was heated to 80 to 90 ° C., and the acid anhydride was dissolved and then cooled, further diluted with water, and solidified. A substituted succinic acid neutralized salt (C-1) having a partial weight of 35% was obtained.
調製例７（置換コハク酸中和塩（Ｃ）の調製）
冷却管、撹拌機の付いたフラスコに、炭素数が１８でありかつ２〜４位に二重結合を有する内部オレフィンに無水マレイン酸を付加してアルケニルコハク酸無水物を得た。この酸無水物１００部に、次いで水酸化カリウム３３．６部を水２１０部に溶解した溶液を加えて系を８０〜９０℃に加温し、該酸無水物を溶解した後冷却し、更に水で希釈して、固形分重量が３５％の置換コハク酸中和塩（Ｃ−２）を得た。
Preparation Example 7 (Preparation of Substituted Succinic Acid Neutralized Salt (C))
Into a flask equipped with a condenser and a stirrer, maleic anhydride was added to an internal olefin having 18 carbon atoms and a double bond at the 2-4 position to obtain an alkenyl succinic anhydride. A solution prepared by dissolving 33.6 parts of potassium hydroxide in 210 parts of water was added to 100 parts of this acid anhydride, and the system was heated to 80 to 90 ° C., and the acid anhydride was dissolved and then cooled. Dilution with water gave a substituted succinic acid neutralized salt (C-2) having a solid content of 35%.
実施例１〜９、比較例１〜５、参照例
＜試験用塗工液（表面サイズ剤希釈液）の調製＞
前記ケテンダイマー（Ａ−１）〜（Ａ−２）、水溶性共重合体（Ｂ−１）〜（Ｂ−３）、置換コハク酸中和塩（Ｃ−１）〜（Ｃ−２）を用い、表１で示す配合比（固形分換算）で混合したものに、市販澱粉（商品名「王子エースＡ」、王子コーンスターチ（株）製）を表１に示す割合となるように添加し、更に蒸留水で希釈することによって、実施例・比較例用の塗工液を調製した。なお、参照用に、当該市販澱粉を蒸留水で希釈してなる塗工液を調製した。
Examples 1 to 9, Comparative Examples 1 to 5, Reference Example <Preparation of Test Coating Solution (Surface Sizing Agent Dilution Solution)>
The ketene dimers (A-1) to (A-2), water-soluble copolymers (B-1) to (B-3), and substituted succinic acid neutralized salts (C-1) to (C-2). Use, with a mixture ratio shown in Table 1 (solid content conversion), add commercially available starch (trade name “Oji Ace A”, manufactured by Oji Corn Starch Co., Ltd.) to the ratio shown in Table 1, Furthermore, the coating liquid for an Example and a comparative example was prepared by diluting with distilled water. For reference, a coating solution prepared by diluting the commercially available starch with distilled water was prepared.
＜試験用紙の作成＞
中性中質原紙（秤量４５ｇ／ｍ２）を原紙に用い、前記塗工液をゲートロールコーターにより表１で示す塗工量１となるように塗工した。次いで、得られた塗工紙を回転ドラムドライヤーにおいて８０℃で３０秒間乾燥し、目的とする試験用紙を得た。なお、該酸性新聞原紙に澱粉のみを塗工したものを参照例として示す。
<Creation of test paper>
A neutral medium base paper (weighing 45 g / m 2 ) was used as the base paper, and the coating solution was applied by a gate roll coater so as to have a coating amount 1 shown in Table 1. Next, the obtained coated paper was dried at 80 ° C. for 30 seconds in a rotary drum dryer to obtain a target test paper. In addition, what applied only starch to this acidic newspaper base paper is shown as a reference example.
＜ドロップサイズの測定＞
前記方法で得られた各試験用紙を用い、Ｊａｐａｎ ＴＡＰＰＩ Ｎｏ.３３に準拠した方法に基づき、試験用紙表面に水５μｌを滴下し、水滴が紙面に吸収されるまでの時間を測定し、ドロップサイズ（秒）を測定した。数値が高いほど、サイズ効果に優れることを意味する。結果を表１に示す。
<Measurement of drop size>
Using each test paper obtained by the above method, 5 μl of water was dropped on the surface of the test paper based on a method based on Japan TAPPI No. 33, and the time until the water droplet was absorbed on the paper surface was measured. (Seconds) was measured. The higher the value, the better the size effect. The results are shown in Table 1.
＜ネッパリの測定＞
前記方法で得られた各試験用紙を２枚、水に１秒間浸漬し、その後両者を張り合わせたものを、線圧９８０Ｎ／ｃｍのロールに通し、得られた試験用紙を風乾させた後で、引っ張り試験機（商品名「ＬＲＸ」：（株）安田精機商会製）を用いてＴ字剥離強度（Ｎ／ｍ）を測定した。得られた値をネッパリ強度とする。数値が高いほどネッパリが強いことを意味する。結果を表１に示す。
<Measurement of Neppari>
After each test paper obtained by the above method was immersed in water for 1 second and then bonded together, it was passed through a roll having a linear pressure of 980 N / cm, and the obtained test paper was air-dried. T-peel strength (N / m) was measured using a tensile tester (trade name “LRX”: manufactured by Yasuda Seiki Shokai Co., Ltd.). The obtained value is defined as Nepari intensity. A higher number means stronger Nepari. The results are shown in Table 1.
＜表面摩擦係数の測定＞
ＪＩＳ Ｐ ８１４７（１９９４）に記載の水平方法に準拠して、試験用紙の表面摩擦係数（静摩擦係数）を測定した。数値が小さいほど前記紙すべりが抑制されることを意味する。
<Measurement of surface friction coefficient>
In accordance with the horizontal method described in JIS P 8147 (1994), the surface friction coefficient (static friction coefficient) of the test paper was measured. A smaller value means that the paper slip is suppressed.
Claims (7)
A printing paper obtained by coating the paper surface with the paper size sizing agent according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161885A (en) * | 2008-01-08 | 2009-07-23 | Arakawa Chem Ind Co Ltd | Papermaking surface sizing agent |
| JPWO2012090496A1 (en) * | 2010-12-28 | 2014-06-05 | 星光Pmc株式会社 | Water dispersible sizing agent, paper manufacturing method and paperboard manufacturing method |
| JP2021004425A (en) * | 2019-06-26 | 2021-01-14 | 荒川化学工業株式会社 | Surface sizing agent for paper making, method for producing surface sizing agent for paper making and coated paper |
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| JPH09228293A (en) * | 1996-02-28 | 1997-09-02 | Seiko Kagaku Kogyo Co Ltd | Surface-sizing composition for paper making |
| JP2000507651A (en) * | 1996-03-29 | 2000-06-20 | ストゥーラー コーパーバリィス バリィスラーグス アクチエボラーグ（ペーユーベーエル） | Sizing composition, production method and use thereof |
| JP2001518575A (en) * | 1997-09-30 | 2001-10-16 | ハーキュリーズ・インコーポレーテッド | Method for surface sizing paper with cellulose-reactive and non-cellulose-reactive sizing agents, and paper produced thereby |
| WO2004037930A2 (en) * | 2002-10-24 | 2004-05-06 | Spectra-Kote Corporation | Coating compositions comprising alkyl ketene dimers and alkyl succinic anhydrides for use in paper making |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01207495A (en) * | 1988-02-16 | 1989-08-21 | Dic Hercules Chem Inc | Production of paper |
| JPH09228293A (en) * | 1996-02-28 | 1997-09-02 | Seiko Kagaku Kogyo Co Ltd | Surface-sizing composition for paper making |
| JP2000507651A (en) * | 1996-03-29 | 2000-06-20 | ストゥーラー コーパーバリィス バリィスラーグス アクチエボラーグ（ペーユーベーエル） | Sizing composition, production method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161885A (en) * | 2008-01-08 | 2009-07-23 | Arakawa Chem Ind Co Ltd | Papermaking surface sizing agent |
| JPWO2012090496A1 (en) * | 2010-12-28 | 2014-06-05 | 星光Pmc株式会社 | Water dispersible sizing agent, paper manufacturing method and paperboard manufacturing method |
| JP2021004425A (en) * | 2019-06-26 | 2021-01-14 | 荒川化学工業株式会社 | Surface sizing agent for paper making, method for producing surface sizing agent for paper making and coated paper |
| JP7287148B2 (en) | 2019-06-26 | 2023-06-06 | 荒川化学工業株式会社 | Surface sizing agent for papermaking, method for producing surface sizing agent for papermaking, and coated paper |
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